TWI526447B - A photonic agent composition containing a sorbitol compound, and a method for producing a polypropylene resin composition using the sorbitol compound - Google Patents
A photonic agent composition containing a sorbitol compound, and a method for producing a polypropylene resin composition using the sorbitol compound Download PDFInfo
- Publication number
- TWI526447B TWI526447B TW100108795A TW100108795A TWI526447B TW I526447 B TWI526447 B TW I526447B TW 100108795 A TW100108795 A TW 100108795A TW 100108795 A TW100108795 A TW 100108795A TW I526447 B TWI526447 B TW I526447B
- Authority
- TW
- Taiwan
- Prior art keywords
- mass
- polypropylene resin
- butyl
- polypropylene
- dibenzylidene sorbitol
- Prior art date
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- -1 sorbitol compound Chemical class 0.000 title claims description 123
- 239000000203 mixture Substances 0.000 title claims description 44
- 239000004743 Polypropylene Substances 0.000 title claims description 40
- 229920001155 polypropylene Polymers 0.000 title claims description 40
- 239000003795 chemical substances by application Substances 0.000 title claims description 38
- 239000011342 resin composition Substances 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 title description 11
- 239000000600 sorbitol Substances 0.000 title description 11
- 229920005989 resin Polymers 0.000 claims description 49
- 239000011347 resin Substances 0.000 claims description 49
- 229940087101 dibenzylidene sorbitol Drugs 0.000 claims description 47
- FMZUHGYZWYNSOA-VVBFYGJXSA-N (1r)-1-[(4r,4ar,8as)-2,6-diphenyl-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C([C@@H]1OC(O[C@@H]([C@@H]1O1)[C@H](O)CO)C=2C=CC=CC=2)OC1C1=CC=CC=C1 FMZUHGYZWYNSOA-VVBFYGJXSA-N 0.000 claims description 22
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 17
- 229920005673 polypropylene based resin Polymers 0.000 claims description 15
- 238000001125 extrusion Methods 0.000 claims description 9
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 description 17
- 239000002184 metal Substances 0.000 description 17
- 239000000843 powder Substances 0.000 description 17
- 230000000694 effects Effects 0.000 description 16
- 238000012545 processing Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 12
- 230000000704 physical effect Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- 239000003963 antioxidant agent Substances 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- 239000003063 flame retardant Substances 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 230000003078 antioxidant effect Effects 0.000 description 8
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 239000002667 nucleating agent Substances 0.000 description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 7
- 238000010298 pulverizing process Methods 0.000 description 7
- 238000011282 treatment Methods 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- XQBHFKDMCJYDIV-UHFFFAOYSA-N C(C)(C)(C)C=1C=C(C=C(C1O)C(C)(C)C)CCCOCC(COCCCC1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C)(COCCCC1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C)COCCCC1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C Chemical compound C(C)(C)(C)C=1C=C(C=C(C1O)C(C)(C)C)CCCOCC(COCCCC1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C)(COCCCC1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C)COCCCC1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C XQBHFKDMCJYDIV-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 229960001545 hydrotalcite Drugs 0.000 description 4
- 229910001701 hydrotalcite Inorganic materials 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 239000002530 phenolic antioxidant Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 125000005767 propoxymethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])[#8]C([H])([H])* 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920002620 polyvinyl fluoride Polymers 0.000 description 3
- 229920001384 propylene homopolymer Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- ODJQKYXPKWQWNK-UHFFFAOYSA-L 3-(2-carboxylatoethylsulfanyl)propanoate Chemical compound [O-]C(=O)CCSCCC([O-])=O ODJQKYXPKWQWNK-UHFFFAOYSA-L 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 239000012773 agricultural material Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical class [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 description 2
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 229920005606 polypropylene copolymer Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- YEYCMBWKTZNPDH-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) benzoate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)C1=CC=CC=C1 YEYCMBWKTZNPDH-UHFFFAOYSA-N 0.000 description 1
- MCEIDHMFDKXAPA-UHFFFAOYSA-N (2-tridecylphenyl) dihydrogen phosphite Chemical compound CCCCCCCCCCCCCC1=CC=CC=C1OP(O)O MCEIDHMFDKXAPA-UHFFFAOYSA-N 0.000 description 1
- ABFCPWCUXLLRSC-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol Chemical compound C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C ABFCPWCUXLLRSC-UHFFFAOYSA-N 0.000 description 1
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 description 1
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- SVNVBMPPWVBFTL-UHFFFAOYSA-N 1,4-bis(2,2,6,6-tetramethylpiperidin-4-yl)-2,3-di(tridecyl)butane-1,2,3,4-tetracarboxylic acid Chemical compound CCCCCCCCCCCCCC(C(C1CC(NC(C1)(C)C)(C)C)C(=O)O)(C(=O)O)C(CCCCCCCCCCCCC)(C(C2CC(NC(C2)(C)C)(C)C)C(=O)O)C(=O)O SVNVBMPPWVBFTL-UHFFFAOYSA-N 0.000 description 1
- ITAMCOCNZJPJDF-UHFFFAOYSA-N 1-(6-aminopurin-9-yl)propan-2-yloxymethyl-phenoxyphosphinic acid Chemical compound C1=NC2=C(N)N=CN=C2N1CC(C)OCP(O)(=O)OC1=CC=CC=C1 ITAMCOCNZJPJDF-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- FGQBMYYYVDAGNF-UHFFFAOYSA-N 2,2,6,6-tetramethyl-4-[6-(2,2,6,6-tetramethylpiperidin-4-yl)hexyl]piperidine Chemical compound C1C(C)(C)NC(C)(C)CC1CCCCCCC1CC(C)(C)NC(C)(C)C1 FGQBMYYYVDAGNF-UHFFFAOYSA-N 0.000 description 1
- PFEFOYRSMXVNEL-UHFFFAOYSA-N 2,4,6-tritert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 PFEFOYRSMXVNEL-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- MFZAXZRJGHLULL-UHFFFAOYSA-N 2,4-ditert-butyl-6-[2-(3,5-ditert-butyl-2-hydroxyphenyl)ethyl]phenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(CCC=2C(=C(C=C(C=2)C(C)(C)C)C(C)(C)C)O)=C1O MFZAXZRJGHLULL-UHFFFAOYSA-N 0.000 description 1
- QJIIIQKTRUDEHY-UHFFFAOYSA-N 2-[2-(benzotriazol-2-yl)phenyl]-4,6-di(propan-2-yl)phenol Chemical compound OC1=C(C=C(C=C1C(C)C)C(C)C)C1=C(C=CC=C1)N1N=C2C(=N1)C=CC=C2 QJIIIQKTRUDEHY-UHFFFAOYSA-N 0.000 description 1
- ZSMMOCNTIRCAAL-UHFFFAOYSA-N 2-[2-[2-[2-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 2-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound C=1C(C)=C(O)C(C(C)(C)C)=CC=1C(C)C(=O)OCCOCCOCCOC(=O)C(C)C1=CC(C)=C(O)C(C(C)(C)C)=C1 ZSMMOCNTIRCAAL-UHFFFAOYSA-N 0.000 description 1
- WVQHODUGKTXKQF-UHFFFAOYSA-N 2-ethyl-2-methylhexane-1,1-diol Chemical compound CCCCC(C)(CC)C(O)O WVQHODUGKTXKQF-UHFFFAOYSA-N 0.000 description 1
- ROIMNSWDOJCBFR-UHFFFAOYSA-N 2-iodothiophene Chemical compound IC1=CC=CS1 ROIMNSWDOJCBFR-UHFFFAOYSA-N 0.000 description 1
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
- NYKHQQHUHLNYLW-UHFFFAOYSA-N tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) butane-1,1,1,2-tetracarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)C(C(=O)OC1CC(C)(C)NC(C)(C)C1)(C(=O)OC1CC(C)(C)NC(C)(C)C1)C(CC)C(=O)OC1CC(C)(C)NC(C)(C)C1 NYKHQQHUHLNYLW-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- JNPQFTCBVDSMDO-UHFFFAOYSA-L zinc;2,3-dihydroxypropanoate Chemical compound [Zn+2].OCC(O)C([O-])=O.OCC(O)C([O-])=O JNPQFTCBVDSMDO-UHFFFAOYSA-L 0.000 description 1
- GAMIYQSIKAOVTG-UHFFFAOYSA-L zinc;2-aminopentanedioate Chemical compound [Zn+2].[O-]C(=O)C(N)CCC([O-])=O GAMIYQSIKAOVTG-UHFFFAOYSA-L 0.000 description 1
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Description
本發明係關於一種透明化劑組合物,其於將先前被認為不適合在加工聚丙烯系樹脂時添加之粒徑較大之二亞苄基山梨糖醇系透明化劑與樹脂混合之前,預先與特定之酚系抗氧化劑混合,然後將該混合物添加於樹脂中,藉此可成形透明性優異之聚丙烯系樹脂組合物。
又,本發明係關於一種透明性優異之聚丙烯系樹脂組合物之製造方法,其藉由選擇特定之加工條件,而可調配先前被認為不適合於在加工聚丙烯系樹脂時添加之粒徑較大之二亞苄基山梨糖醇系透明化劑。
丙烯均聚物或乙烯-丙烯共聚物等聚丙烯系樹脂被廣泛地用於汽車、家電、建築材料、傢具、包裝容器、玩具、日用雜貨等。然而,由於聚丙烯系樹脂於透明性方面劣於聚乙烯、聚對苯二甲酸乙二酯、聚碳酸酯、聚苯乙烯等,故而自先前以來即提出調配苯甲酸金屬鹽、芳香族磷酸酯金屬鹽、脂肪族環狀化合物之金屬鹽或二亞苄基山梨糖醇類、醯胺化合物等各種成核劑、透明化劑之方法並已實用化。
其中,二亞苄基山梨糖醇類雖然改善透明性之效果優異,然而存在臭氣強烈,熔點較高,難以於加工溫度下均勻地分散於樹脂中等缺點。雖然藉由使加工溫度為熔點以上可實現均勻分散,然而本發明中所使用之通式(I)所表示之化合物之熔點高如260℃以上,於熔點以上進行加工會引起聚丙烯顯著劣化,故而不佳。為提高於熔點以下朝樹脂中之分散性,提出有藉由粉碎而使粒徑變小,或者預先與其他成分熔融混合而使熔點降低等各種處理。
例如,於專利文獻1中提出有,藉由使二亞苄基山梨糖醇類成為d97為30 μm以下之粉末而使之表現性能。該二亞苄基山梨糖醇類雖然改善透明性之效果優異,然而由於成為微粉,流動性降低,因此除計量、添加等之操作性降低以外,亦存在由於結塊而無法獲得所期待之分散性等問題。又,經微粉碎而成者實際上必需利用無機物或表面處理劑等來防止二次凝集,不但製造成本增加,並且會於樹脂中混合並不需要之成分。無意地混合不需要之成分會伴隨樹脂物性變化,或者成為再利用時品質下降或用途受限之原因,因此,微粉化並非令人滿意之解決方法。
於專利文獻2中提出有,藉由使用不同結構之二亞苄基山梨糖醇化合物的混合物而使性能提高。藉由形成為類似結構物之混合物會使熔點降低,故而朝樹脂中之分散性提高。然而,其係於二亞苄基山梨糖醇類中的效果特別優異之化合物中添加其他結構之透明化劑者,使透明化效果降低等,未必為充分之解決對策。
又,由於單獨之聚丙烯於加工溫度下會劣化,故而必需調配酚系抗氧化劑或磷系抗氧化劑等添加劑成分,自先前以來,一直係將該等添加劑成分與成核劑或透明化劑一起調配至聚丙烯之粉末或顆粒中。如專利文獻1中作為比較例所揭示般,即便將該等其他添加劑成分與二亞苄基山梨糖醇類一起調配至樹脂中,利用亨舍爾混合機(Henschel mixer)等加以混合,亦無法提高二亞苄基山梨糖醇類之分散性。
專利文獻
專利文獻1:日本專利特開平06-145431號公報
專利文獻2:日本專利特開平02-206627號公報
本發明之目的在於提供一種二亞苄基山梨糖醇系透明化劑,其可並不將二亞苄基山梨糖醇化合物微粉化地調配於聚丙烯系樹脂中,而形成透明性優異之聚丙烯系樹脂組合物。
又,本發明之目的在於提供一種即便不將亞苄基山梨糖醇化合物微粉化地調配於聚丙烯系樹脂中,亦具有優異之透明性及物性的聚丙烯系樹脂組合物之製造方法。
本發明藉由提供如下之透明化劑組合物而達成上述目的,該透明化劑組合物係粒徑中d97為30 μm以上且200 μm以下之下述通式(I)所表示之二亞苄基山梨糖醇化合物100質量份、與四[3-(3,5-二-第三丁基-4-羥基苯基)丙醯氧基甲基]甲烷5~200質量份之混合物,且兩成分之合計為混合物之50質量%以上。
又,本發明藉由提供如下之聚丙烯系樹脂組合物之製造方法而達成上述目的,該製造方法之特徵在於:於獲得在聚丙烯系樹脂中調配有粒徑中d97為30 μm以上且200 μm以下之下述通式(I)所表示之二亞苄基山梨糖醇化合物的聚丙烯系樹脂組合物時,使用雙軸擠出機,於擠出溫度220~250℃下混練於上述聚丙烯系樹脂100質量份中調配有上述二亞苄基山梨糖醇化合物0.05~2質量份之混合物。
[化1]
首先,對本發明之透明化劑組合物進行說明。用於本發明之透明化劑組合物的通式(I)所表示之二亞苄基山梨糖醇化合物對其製造方法並無特別限定,可為利用公知之任意方法所得者。
用於本發明之透明化劑組合物之通式(I)所表示之二亞苄基山梨糖醇化合物的粒徑中,d97為30 μm以上、200 μm以下,較佳為d97為40 μm以上、150 μm以下,尤佳為d97為40 μm以上、100 μm以下。由於粉碎至d97未達30 μm不僅粉碎成本升高,而且會產生結塊從而操作性降低,且向樹脂中之分散性亦降低,故而不佳。若d97大於200 μm,則存在透明性不充分,或成形為膜等時魚眼增加等問題。再者,本發明中之所謂d97,係指小於某一粒徑之粒子量相對於全部粒子量之百分率為97的粒徑。
用於本發明之透明化劑組合物之四[3-(3,5-二-第三丁基-4-羥基苯基)丙醯氧基甲基]甲烷包括其中間物可不限定製造方法、晶形、熔點、紅外線吸收光譜、X射線繞射波峰等而使用。
本發明之透明化劑組合物係於通式(I)所表示之二亞苄基山梨糖醇化合物100質量份中混合四[3-(3,5-二-第三丁基-4-羥基苯基)丙醯氧基甲基]甲烷5~200質量份,較佳為10~150質量份而成者,混合裝置或溫度等混合條件等並無特別限制,可使用亨舍爾混合機等各種混合裝置。由於無需特別使其熔融,故而較佳為於室溫下進行混合,而不進行加熱或冷卻等會引起成本增加之處理。並且,若在室溫下混合,則不存在混合時著色之虞,故而較佳。又,為抑制與樹脂加熱混練時因氧化而引起著色,亦可於氮氣環境下進行混合處理。
本發明之透明化劑組合物中,通式(I)所表示之二亞苄基山梨糖醇化合物與四[3-(3,5-二-第三丁基-4-羥基苯基)丙醯氧基甲基]甲烷之兩成分之合計為混合物之50質量%以上,較佳為80質量%以上,尤佳為100質量%。
作為可調配於本發明之透明化劑組合物中的上述兩成分以外之成分,可列舉抗氧化劑、受阻胺化合物、其他成核劑等。
本發明之透明化劑組合物對於提高聚丙烯系樹脂之透明性有效,作為聚丙烯系樹脂,可列舉:丙烯均聚物、乙烯-丙烯無規共聚物、乙烯-丙烯嵌段共聚物、丙烯與少量(1~10質量%)之其他α-烯烴(例如1-丁烯、1-己烯、4-甲基-1-戊烯等)之共聚物、丙烯與乙烯丙烯之共聚物(TPO)等。
上述聚丙烯系樹脂可無論聚合觸媒‧助觸媒之種類或有無、立體規則性、平均分子量、分子量分佈、特定分子量成分之有無或比率、比重、黏度、於各種溶劑中之溶解度、伸長係數、衝擊強度、結晶度、X射線繞射、藉由不飽和羧酸(順丁烯二酸、伊康酸、反丁烯二酸等)及其衍生物(順丁烯二酸酐、順丁烯二酸單酯、順丁烯二酸二酯等)或有機過氧化物或者能量線之照射以及該等處理之組合所引起的改質‧交聯處理之有無等而使用。
本發明之透明化劑組合物較佳為相對於聚丙烯系樹脂100質量份調配0.01~10質量份,更佳為調配0.05~5質量份。
於本發明之調配有透明化劑組合物之聚丙烯系樹脂組合物中,較佳為根據使用條件或要求特性而添加酚系抗氧化劑、磷系抗氧化劑、硫系抗氧化劑、紫外線吸收劑、受阻胺化合物、阻燃劑、阻燃助劑、其他成核劑、抗靜電劑、重金屬鈍化劑、塑化劑、軟化劑、潤滑劑、水滑石化合物、脂肪酸金屬鹽、顏料、紅外線吸收劑、防滴劑、防霧劑、填充劑、抗菌‧抗黴劑等通用之樹脂添加劑。
作為酚系抗氧化劑,可列舉:2,6-二-第三丁基-對甲酚、2,6-二苯基-4-十八烷氧基苯酚、2-甲基-4,6-雙(辛硫基甲基)苯酚、二硬脂基(3,5-二-第三丁基-4-羥基苄基)膦酸酯、1,6-六亞甲基雙[(3,5-二-第三丁基-4-羥基苯基)丙醯胺]、4,4'-硫代雙(6-第三丁基-間甲酚)、2,2'-亞甲基雙(4-甲基-6-第三丁基苯酚)、2,2'-亞甲基雙(4-乙基-6-第三丁基苯酚)、4,4'-亞丁基雙(6-第三丁基-間甲酚)、2,2'-亞乙基雙(4,6-二-第三丁基苯酚)、2,2'-亞乙基雙(4-第二丁基-6-第三丁基苯酚)、1,1,3-三(2-甲基-4-羥基-5-第三丁基苯基)丁烷、1,3,5-三(2,6-二甲基-3-羥基-4-第三丁基苄基)異氰尿酸酯、1,3,5-三(3,5-二-第三丁基-4-羥基苄基)異氰尿酸酯、1,3,5-三(3,5-二-第三丁基-4-羥基苄基)-2,4,6-三甲基苯、2-第三丁基-4-甲基-6-(2-丙烯醯氧基-3-第三丁基-5-甲基苄基)苯酚、硬脂基(3,5-二-第三丁基-4-羥基苯基)丙酸酯、硫代二乙二醇雙[(3,5-二-第三丁基-4-羥基苯基)丙酸酯]、1,6-六亞甲基雙[(3,5-二-第三丁基-4-羥基苯基)丙酸酯]、雙[3,3-雙(4-羥基-3-第三丁基苯基)丁酸]乙二醇酯、雙[2-第三丁基-4-甲基-6-(2-羥基-3-第三丁基-5-甲基苄基)苯基]對苯二甲酸酯、1,3,5-三[(3,5-二-第三丁基-4-羥基苯基)丙醯氧基乙基]異氰尿酸酯、四[3-(3,5-二-第三丁基-4-羥基苯基)丙酸甲酯]甲烷、3,9-雙[1,1-二甲基-2-{(3-第三丁基-4-羥基-5-甲基苯基)丙醯氧基}乙基]-2,4,8,10-四氧雜螺[5.5]十一烷、三乙二醇雙[(3-第三丁基-4-羥基-5-甲基苯基)丙酸酯]等,相對於樹脂100重量份,較佳為使用0.001~10重量份,更佳為使用0.05~5重量份。
作為磷系抗氧化劑,例如可列舉:亞磷酸三壬基苯酯、亞磷酸三(2,4-二-第三丁基苯基)酯、亞磷酸三[2-第三丁基-4-(3-第三丁基-4-羥基-5-甲基苯硫基)-5-甲基苯基]酯、亞磷酸十三烷基酯、亞磷酸辛基二苯酯、亞磷酸二(癸基)單苯酯、二(十三烷基)季戊四醇二亞磷酸酯、二(壬基苯基)季戊四醇二亞磷酸酯、雙(2,4-二-第三丁基苯基)季戊四醇二亞磷酸酯、雙(2,6-二-第三丁基-4-甲基苯基)季戊四醇二亞磷酸酯、雙(2,4,6-三-第三丁基苯基)季戊四醇二亞磷酸酯、雙(2,4-二異丙苯基苯基)季戊四醇二亞磷酸酯、四(十三烷基)亞異丙基雙苯酚二亞磷酸酯、四(十三烷基)-4,4'-正亞丁基雙(2-第三丁基-5-甲基苯酚)二亞磷酸酯、六(十三烷基)-1,1,3-三(2-甲基-4-羥基-5-第三丁基苯基)丁烷三亞磷酸酯、四(2,4-二-第三丁基苯基)伸聯苯基二亞磷酸酯、9,10-二氫-9-雜氧-10-磷雜菲-10-氧化物、2,2'-亞甲基雙(4,6-第三丁基苯基)-2-乙基已基亞磷酸酯、2,2'-亞甲基雙(4,6-第三丁基苯基)-十八烷基亞磷酸酯、2,2'-亞乙基雙(4,6-二-第三丁基苯基)氟亞磷酸酯、三(2-[(2,4,8,10-四-第三丁基二苯并[d,f][1,3,2]二磷環庚烷-6-基)氧基]乙基)胺、2-乙基-2-丁基丙二醇與2,4,6-三-第三丁基苯酚之亞磷酸酯等。
作為硫系抗氧化劑,可列舉:硫代二丙酸二月桂酯、硫代二丙酸二肉豆蔻酯、硫代二丙酸二棕櫚酯、硫代二丙酸二硬脂基酯、四(3-月桂基硫代二丙酸甲酯)甲烷、雙(2-甲基-4-(烷基(C8~C18單獨或混合)硫代丙醯氧基)-5-第三丁基苯基)硫化物、2-巰基苯并咪唑及其鋅鹽等。
作為紫外線吸收劑,可列舉:2,4-二羥基二苯甲酮、2-羥基-4-甲氧基二苯甲酮、2-羥基-4-辛氧基二苯甲酮、5,5'-亞甲基雙(2-羥基-4-甲氧基二苯甲酮)等2-羥基二苯甲酮類;2-(2'-羥基-5'-甲基苯基)苯并三唑、2-(2'-羥基-3',5'-二-第三丁基苯基)-5-氯苯并三唑、2-(2'-羥基-3'-第三丁基-5'-甲基苯基)-5-氯苯并三唑、2-(2'-羥基-5'-第三辛基苯基)苯并三唑、2-(2'-羥基-3',5'-二異丙苯基苯基)苯并三唑、2,2'-亞甲基雙(4-第三辛基-6-苯并三唑基)苯酚、2-(2'-羥基-3'-第三丁基-5'-羧基苯基)苯并三唑等2-(2'-羥基苯基)苯并三唑類;水楊酸苯酯、間苯二酚單苯甲酸酯、2,4-二-第三丁基苯基-3,5-二-第三丁基-4-羥基苯甲酸酯、2,4-二-第三戊基苯基-3,5-二-第三丁基-4-羥基苯甲酸酯、十六烷基-3,5-二-第三丁基-4-羥基苯甲酸酯等苯甲酸酯類;2-乙基-2'-乙氧基草醯替苯胺、2-乙氧基-4'-十二烷基草醯替苯胺等取代草醯替苯胺類;乙基-α-氰基-β,β-二苯基丙烯酸酯、甲基-2-氰基-3-甲基-3-(對甲氧基苯基)丙烯酸酯等氰基丙烯酸酯類;2-(2-羥基-4-辛氧基苯基)-4,6-雙(2,4-二-第三丁基苯基)-均三、2-(2-羥基-4-甲氧基苯基)-4,6-二苯基-均三、2-(2-羥基-4-丙氧基-5-甲基苯基)-4,6-雙(2,4-二-第三丁基苯基)-均三等三芳基三類。
作為受阻胺化合物,例如可列舉:2,2,6,6-四甲基-4-哌啶基硬脂酸酯、1,2,2,6,6-五甲基-4-哌啶基硬脂酸酯、2,2,6,6-四甲基-4-哌啶基苯甲酸酯、雙(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、雙(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯、雙(1-十一烷氧基-2,2,6,6-四甲基-4-哌啶基)碳酸酯、四(2,2,6,6-四甲基-4-哌啶基)丁烷四甲酸酯、四(1,2,2,6,6-五甲基-4-哌啶基)丁烷四甲酸酯、雙(2,2,6,6-四甲基-4-哌啶基)-二(十三烷基)-1,2,3,4-丁烷四甲酸酯、雙(1,2,2,6,6-五甲基-4-哌啶基)-二(十三烷基)-1,2,3,4-丁烷四甲酸酯、雙(1,2,2,6,6-五甲基-4-哌啶基)-2-丁基-2-(3,5-二-第三丁基-4-羥基苄基)丙二酸酯、1-(2-羥基乙基)-2,2,6,6-四甲基-4-哌啶醇/琥珀酸二乙酯縮聚物、1,6-雙(2,2,6,6-四甲基-4-哌啶基胺基)己烷/二溴乙烷縮聚物、1,6-雙(2,2,6,6-四甲基-4-哌啶基胺基)己烷/2,4-二氯-6-啉基-均三縮聚物、1,6-雙(2,2,6,6-四甲基-4-哌啶基胺基)己烷/2,4-二氯-6-第三辛基胺基-均三縮聚物、1,5,8,12-四[2,4-雙(N-丁基-N-(2,2,6,6-四甲基-4-哌啶基)胺基)-均三-6-基]-1,5,8,12-四氮雜癸烷、1,5,8,12-四[2,4-雙(N-丁基-N-(1,2,2,6,6-五甲基-4-哌啶基)胺基)-均三-6-基]-1,5,8,12-四氮雜癸烷、1,6,11-三[2,4-雙(N-丁基-N-(2,2,6,6-四甲基-4-哌啶基)胺基)-均三-6-基-胺基十一烷、1,6,11-三[2,4-雙(N-丁基-N-(1,2,2,6,6-五甲基-4-哌啶基)胺基)-均三-6-基-胺基十一烷等受阻胺化合物。
作為阻燃劑,可使用:十溴二苯醚或四溴雙酚A等鹵系阻燃劑,磷酸三苯酯、間苯二酚或雙酚A等多元酚與苯酚或2,6-二甲苯酚等一元酚之縮合磷酸酯;赤磷、三聚氰胺磷酸酯等無機磷化合物;三聚氰胺氰尿酸酯等含氮阻燃劑;氫氧化鎂或氫氧化鋁等無機系阻燃劑;氧化銻或氧化鋯等阻燃助劑;聚四氟乙烯等抗滴落劑等。
作為阻燃助劑,可列舉:聚四氟乙烯(PTFE,Polytetrafluoroethene)、聚偏二氟乙烯(PVDF,Polyvinylidene Fluoride)、聚氟乙烯(PVF,Polyvinyl Fluoride)、聚四氟乙烯-六氟丙烯共聚物(FEP,Fluorinated Ethylene Propylene)、(甲基)丙烯酸改質PTFE等氟樹脂或矽樹脂等。
作為其他成核劑,可列舉:苯甲酸鈉、對第三丁基苯甲酸鋁、對第三丁基苯甲酸鋰等苯甲酸類之金屬鹽;2,2-亞甲基雙(4,6-二-第三丁基苯基)磷酸酯鈉等磷酸酯金屬鹽;二亞苄基山梨糖醇、雙(4-甲基亞苄基)山梨糖醇、雙(4-乙基亞苄基)山梨糖醇等其他亞苄基山梨糖醇類;甘油鋅等金屬醇化物類;麩胺酸鋅等胺基酸金屬鹽;雙環庚烷二甲酸或其鹽等具有雙環結構之脂肪族二元酸及其金屬鹽,苯磺酸鈉、對甲苯磺酸鋰等芳香族磺酸金屬鹽等。
本發明係即便不微粉碎而使用對賦予透明性特別優異之通式(I)之二亞苄基山梨糖醇化合物,亦可獲得與微粉碎品同等之效果者,且若併用其他二亞苄基山梨糖醇類,則與添加量相比而言透明性之提高效果較小,故而本發明之效果會降低。若與如2,2-亞甲基雙(4,6-二-第三丁基苯基)磷酸酯鈉等磷酸酯金屬鹽等金屬鹽系化合物般之不僅可提高透明性且亦可提高聚丙烯系樹脂之玻璃轉移溫度的成核劑併用,則可期待僅利用本發明所無法獲得之效果,故而較佳。
作為重金屬鈍化劑,例如可列舉:2-羥基苯甲醯胺-N-1H-1,2,4-三唑-3-基或十二烷二酸雙[2-(2-羥基苯甲醯基)醯肼]等。
作為水滑石化合物,較佳使用下述通式(II)所表示之包含鎂及鋁之複鹽化合物,或者包含鎂、鋅及鋁之複鹽化合物,又,亦可為將結晶水脫水後者。
Mgx1Znx2Al2‧(OH)2(x1+x2)+4‧(CO3)1-y1/2‧mH2O (II)
(式中,x1、x2及y1分別表示滿足下述式所示之條件的數,m表示0或任意之整數。
0≦x2/x1≦10、2≦x1+x2<20、0≦y1≦2)
上述水滑石化合物可為天然產物,亦可為合成品。作為該合成品之合成方法,可例示日本專利特公昭46-2280號公報、日本專利特公昭50-30039號公報、日本專利特公昭51-29129號公報、日本專利特公平3-36839號公報、日本專利特開昭61-174270號公報、日本專利特開2001-164042號公報、日本專利特開2002-53722號公報等中所揭示之公知之合成方法。又,於本發明中,上述水滑石化合物可不限制其結晶結構、結晶粒徑等而使用,且原料中所含之鐵等重金屬成分之殘留量較佳為在純化成本實用之範圍內較少。
又,作為上述水滑石化合物,可使用其表面由以下物質被覆者:如硬脂酸之高級脂肪酸、如油酸鹼金屬之高級脂肪酸金屬鹽、如十二烷基苯磺酸鹼金屬鹽之有機磺酸金屬鹽、高級脂肪酸醯胺、高級脂肪酸酯或蠟等。
將本發明之透明化劑組合物調配於聚丙烯系樹脂中之方法、調配所得之樹脂組合物之成形方法、用途等並無特別限制,可使用擠出成形、射出成形、吹塑、壓延、擠壓成形、真空成形等公知之成形加工技術,成形為膜、薄板、成形品等而用於汽車之內外裝飾材料、家電製品、建築材料、包裝材料、農業用材料、雜貨、醫療用器具等,至於使用形態,可單獨使用或者直接或經由接著劑層於其他樹脂或金屬等上貼合等後使用。
其次,對本發明之聚丙烯系樹脂組合物之製造方法進行說明。作為本發明之聚丙烯系樹脂組合物之製造方法所使用的聚丙烯系樹脂,可列舉:丙烯均聚物、乙烯-丙烯無規共聚物、乙烯-丙烯嵌段共聚物、丙烯與少量(1~10質量%)之其他α-烯烴(例如,1-丁烯、1-己烯、4-甲基-1-戊烯等)之共聚物、丙烯與乙烯丙烯之共聚物(TPO)等。
上述聚丙烯系樹脂可無論聚合觸媒‧助觸媒之種類或有無、立體規則性、平均分子量、分子量分佈、特定之分子量成分之有無或比率、比重、黏度、於各種溶劑中之溶解度、伸長係數、衝擊強度、結晶度、X射線繞射、藉由不飽和羧酸(順丁烯二酸、伊康酸、反丁烯二酸等)及其衍生物(順丁烯二酸酐、順丁烯二酸單酯、順丁烯二酸二酯等)或有機過氧化物或者能量線之照射及該等處理之組合所引起的改質‧交聯處理之有無等而使用。
本發明之聚丙烯系樹脂組合物之製造方法所使用的通式(I)所表示之二亞苄基山梨糖醇化合物對其製造方法並無特別限定,可為利用公知之任意方法所得者。
本發明之製造方法所使用的通式(I)所表示之二亞苄基山梨糖醇化合物之粒徑中,d97為30 μm以上、200 μm以下,尤佳為d97為40 μm以上、150 μm以下。由於粉碎至d97未達30 μm不僅粉碎成本升高,而且會產生結塊從而操作性降低,故而不佳。若d97大於200 μm,則存在透明性不充分,或者成形為膜等時魚眼增加等問題。再者,本發明中之所謂d97,係指小於某一粒徑之粒子量相對於全部粒子量之百分率為97的粒徑。
上述通式(I)所表示之二亞苄基山梨糖醇化合物之調配量相對於上述聚丙烯系樹脂100質量份為0.05~2質量份,較佳為0.1~1質量份。若二亞苄基山梨糖醇化合物之調配量未達0.05質量份,則添加效果不充分,另外,即便添加超過2質量份,亦未發現效果提高。
作為混練於上述聚丙烯系樹脂中調配有上述通式(I)所表示之二亞苄基山梨糖醇化合物之混合物的雙軸擠出機,較佳為自樹脂投入部至模具包含至少3個溫度管理區域者,例如可較佳地使用池貝股份有限公司製造之雙軸擠出機PCM-30(商品名)、日本製鋼所股份有限公司製造之雙軸擠出機TEX-28V(商品名)等。
藉由上述雙軸擠出機混練混合物係於擠出溫度為220~250℃,較佳為230~250℃下進行。雙軸擠出機之溫度設定只要設定為自雙軸擠出機之樹脂投入部至模具之區域中樹脂投入部以外,且模具以外之部分之溫度為220~250℃即可。
若擠出溫度未達220℃,則分散性變差,難以表現出效果,另外,若超過250℃,則會引起聚丙烯系樹脂劣化,故而不佳。
在上述聚丙烯系樹脂中調配上述通式(I)所表示之二亞苄基山梨糖醇化合物時,較佳為將該二亞苄基山梨糖醇化合物及四[3-(3,5-二-第三丁基-4-羥基苯基)丙醯氧基甲基]甲烷以混合物之形態調配,或者將該等化合物分別分開且同時調配。於調配四[3-(3,5-二-第三丁基-4-羥基苯基)丙醯氧基甲基]甲烷之情形時,相對於上述二亞苄基山梨糖醇化合物100質量份,較佳為調配5~200質量份,尤佳為10~150質量份。
又,在上述聚丙烯系樹脂中調配有上述通式(I)所表示之二亞苄基山梨糖醇化合物之混合物中,較佳為根據本發明之聚丙烯系樹脂組合物之使用條件或要求特性而添加酚系抗氧化劑、磷系抗氧化劑、硫系抗氧化劑、紫外線吸收劑、受阻胺化合物、阻燃劑、阻燃助劑、其他成核劑、抗靜電劑、重金屬鈍化劑、塑化劑、軟化劑、潤滑劑、水滑石化合物、脂肪酸金屬鹽、顏料、紅外線吸收劑、防滴劑、防霧劑、填充劑、抗菌‧抗黴劑等通用之樹脂添加劑。作為該等樹脂添加劑之具體例,可使用上述者。
本發明之聚丙烯系樹脂組合物之成形方法、用途等並無特別限制,可使用擠出成形、射出成形、吹塑、壓延、擠壓成形、真空成形等公知之成形加工技術,成形為膜、薄板、成形品等而用於汽車之內外裝飾材料、家電製品、建築材料、包裝材料、農業用材料、雜貨、醫療用器具等,至於使用形態,可單獨使用或者直接或經由接著劑層於其他樹脂或金屬等上貼合等後使用。
合成例(通式(I)所表示之二亞苄基山梨糖醇化合物之合成)
於反應用四口燒瓶中添加3,4-二甲基苯甲醛44 g(0.42 mol)、山梨糖醇38 g(0.21 mol)、作為觸媒之50%硫酸5 g、作為溶劑之環己烷700 ml及甲醇70 ml,於甲醇回流溫度下攪拌。隨時滴加與揮發之甲醇量等量之甲醇,反應5小時而獲得塊狀物。
利用異丙醇/水=1/1(體積比)洗淨獲得之塊狀物,於90℃下減壓乾燥過濾物。
利用粉碎機粉碎所獲得之塊,藉此分別獲得具有表1及表2所揭示之d97的二亞苄基山梨糖醇粉末(於表1及表2中簡稱為山梨糖醇)。二亞苄基山梨糖醇粉末之d97係藉由雷射光散射而測定。又,對所獲得之二亞苄基山梨糖醇粉末利用粉末試驗機進行安息角測定,從而評價結塊性。將各二亞苄基山梨糖醇粉末之安息角示於表1及表2。安息角越大則表示越缺乏流動性。
實施例1~5及比較例1~3
以表1所揭示之組成,將合成例中所獲得之二亞苄基山梨糖醇粉末(於表1中簡稱為山梨糖醇)與四[3-(3,5-二-第三丁基-4-羥基苯基)丙醯氧基甲基]甲烷之粉末(於表1中簡稱為苯酚,使用ADEKA股份有限公司製造之ADEKA STAB AO-60)混合,分別製備透明化劑組合物。
將該等透明化劑組合物以如下所述之方法調配於聚丙烯系樹脂中而製作試片。再者,比較例3係不製備透明化劑組合物,而將二亞苄基山梨糖醇粉末、四[3-(3,5-二-第三丁基-4-羥基苯基)丙醯氧基甲基]甲烷之粉末與其他樹脂添加劑一起直接調配於聚丙烯系樹脂中。
於無規聚丙烯(MFI(Melt Flow Index,熔融流動指數)=8~10 g/10 min,MG3,Japan Polypropylene(股)製造)100質量份中,調配四[3-(3,5-二-第三丁基-4-羥基苯基)丙醯氧基甲基]甲烷0.1質量份、亞磷酸三(2,4-二-第三丁基苯基)酯0.05質量份、硬脂酸鈣0.05質量份、表1揭示之透明化劑組合物0.3質量份,利用亨舍爾混合機混合,並利用雙軸擠出機(池貝股份有限公司製造,PCM-30)擠出成形而獲得顆粒。於250℃下將所獲得之顆粒射出成形,製作厚度為1 mm之試片。
使用熔融指數測定儀(東洋精機(股)製造),根據JIS K 7210測定所獲得之顆粒於230℃、2.16 kg負載下之熔融流動指數(MFI),評價樹脂物性有無下降。MFI越大者樹脂之物性變化越大,故而不佳。又,根據JIS K 7361-1,測定試片之濁度(Haze),從而測定透明性提高效果。濁度之值越小者透明性越優異,故而較佳。將該等結果示於表1。
根據表1所示之結果可知如下事項。調配有本發明之透明化劑組合物的實施例1~5之聚丙烯系樹脂透明性優異,且物性亦無下降。相對於此,調配有使用粒徑中d97較小之二亞苄基山梨糖醇粉末之透明化劑組合物的比較例1之聚丙烯系樹脂雖然透明性優異,然而物性下降。另外,調配有由二亞苄基山梨糖醇粉末單獨構成之透明化劑組合物的比較例2之聚丙烯系樹脂透明性較差,且物性亦大幅下降。進而,直接調配二亞苄基山梨糖醇粉末與四[3-(3,5-二-第三丁基-4-羥基苯基)丙醯氧基甲基]甲烷之粉末的比較例3之聚丙烯系樹脂的透明性大幅變差。
實施例6~8及比較例4~8
於無規聚丙烯(MFI=8~10 g/10 min,MG3,Japan Polypropylene(股)製造)100質量份中,調配四[3-(3,5-二-第三丁基-4-羥基苯基)丙醯氧基甲基]甲烷0.1質量份、亞磷酸三(2,4-二-第三丁基苯基)酯0.05質量份、硬脂酸鈣0.05質量份、及於合成例中所獲得之具有表2揭示之d97的二亞苄基山梨糖醇粉末0.2質量份,利用亨舍爾混合機混合,並使用表2揭示之擠出機,於表2揭示之擠出溫度下擠出成形,從而獲得顆粒。於250℃下將所獲得之顆粒射出成形,製作厚度為1 mm之試片。
使用熔融指數測定儀(東洋精機(股)製造),根據JIS K 7210測定所獲得之顆粒於230℃、2.16 kg負載下之熔融流動指數(MFI),評價樹脂物性有無下降。MFI越大者樹脂之物性變化越大,故而不佳。又,根據JIS K 7361-1,測定試片之濁度(Haze),從而測定透明性提高效果。濁度之值越小者透明性越優異,故而較佳。將該等結果表示於表2。
根據表2所表示之結果可知如下事項。根據實施例6與比較例5之對比可知,即便為同一組成,利用單軸擠出機時透明性之改善效果較小,使用雙軸擠出機方能發揮本發明之效果。又,根據比較例7及8可知,即便提高加工溫度而提高分散性,但透明性、物性之穩定性方面得到不佳之結果,只有選擇溫度與加工機方能發揮本發明之效果。根據實施例6及8與比較例4之對比可知,藉由採用本發明之加工條件,流動性優異之粒徑較大之二亞苄基山梨糖醇化合物於先前被認為較差之透明性或物性之穩定性方面,顯示出與經微粉化者同等之性能。再者,根據比較例6可知,於使用d97為接近於300 μm之值之二亞苄基山梨糖醇化合物之情形時,即便於本發明之加工條件下,透明性亦較差,故而必需使二亞苄基山梨糖醇化合物之d97為200 μm以下而使用。
根據本發明之透明化劑組合物,藉由於使先前無法獲得充分之透明性的粒徑較大之二亞苄基山梨糖醇化合物成為與特定之酚系抗氧化劑之混合物後,添加於聚丙烯系樹脂中,可不微粉碎二亞苄基山梨糖醇化合物而提供能夠成形透明性優異之聚丙烯系樹脂組合物的透明化劑組合物。
又,根據本發明之聚丙烯系樹脂組合物之製造方法,即便不將二亞苄基山梨糖醇化合物微粉化而調配於聚丙烯系樹脂中,亦可獲得具有優異之透明性及物性的聚丙烯系樹脂組合物。
Claims (3)
- 一種聚丙烯系樹脂組合物之製造方法,其特徵在於:於在聚丙烯系樹脂中調配粒徑中d97為30μm以上且200μm以下之下述通式(I)所表示之二亞苄基山梨糖醇化合物獲得聚丙烯系樹脂組合物時,使用雙軸擠出機,於擠出溫度220~250℃下混練於上述聚丙烯系樹脂100質量份中調配有透明化劑組合物0.01~10質量份之混合物,上述透明化劑組合物,係上述二亞苄基山梨糖醇化合物100質量份與四[3-(3,5-二-第三丁基-4-羥基苯基)丙醯氧基甲基]甲烷5~200質量份之混合物,且兩成分之合計為混合物之50質量%以上:
- 如請求項1之聚丙烯系樹脂組合物之製造方法,其中通式(I)所表示之二亞苄基山梨糖醇化合物之d97為40μm以上且150μm以下。
- 如請求項1或2之聚丙烯系樹脂組合物之製造方法,其中使用自樹脂投入部至模具包含至少3個溫度管理區域之雙軸擠出機作為雙軸擠出機,並且將樹脂投入部以外且模具以外之部分之溫度設定設為220~250℃。
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CN102725348B (zh) | 2014-02-05 |
EP2554591A1 (en) | 2013-02-06 |
CN103554650B (zh) | 2015-11-18 |
US20120296018A1 (en) | 2012-11-22 |
BR112012016841B1 (pt) | 2020-03-31 |
BR112012016841A2 (pt) | 2018-05-08 |
EP2554591A4 (en) | 2013-08-21 |
US20140128520A1 (en) | 2014-05-08 |
CN103554650A (zh) | 2014-02-05 |
TW201139448A (en) | 2011-11-16 |
EP2554591B1 (en) | 2014-12-24 |
CN102725348A (zh) | 2012-10-10 |
WO2011122264A1 (ja) | 2011-10-06 |
KR101874488B1 (ko) | 2018-07-04 |
US9441091B2 (en) | 2016-09-13 |
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